Linear polyesters containing an alkylene diamine group and manufacture thereof



JVFACTURE REOF, Thomas M. and- Jack Li acid (usually in'ester form). with being oriented .ipolymer s; should improv like, buthere'tofore the Uwn edj St e Pat n LINEAR POLYESTERS' CONTAINING ANAL KYLENE DIAMINE GROUP: AND, MANU N.Y., assignors to Eastman Kodak Company,'Rochestiter N.Y., a corporationofNew Jersey g V N0? pawns bn j fi t in 51955 a Claims ci 260 -75)) 1 This invention relates to improved,linearpolyesters and a to the'vmanufactilre thereof and shaped articles prepared therefrom. More particularly,"the invention is concerned with 1 highly polymeric linear polyesterscharacterized by; atregular, rather thana random, structure and'containing regularly recurring amide linkages, and-to; methods ofn akingsueh polyesters frontia new; type 'of monomeric, 'dicarboxylic compound containing amide linkages.' =-s .The linear condensation polymers, generally fall nto' t two'classes; viz'r'the polyesters and the 'polyamides polyesters are condensation productsf-of; onej-or mor'e" glycols with one or more dicarboxylic acids. The. poly-j amides are condensation products of dicarboxyliclacids 2;: 'with'di'amines; Both broad types of 'condensation'zpblymer's in highly polymeric form were'shown'byC arothers inLUzS. 2,071,250, =-The;polyamide "polymers are-best typified by the nylo'n-type' polymers, for which; the ad-.

van tag es and disadvantages are "well :kitown.v 5 More i recently, emphasis-has been 'on developmentioflthe. polyesters}; and among the more widely known polymers of' thrstype-are the condensation: products of tereplithalic olymethylene glycol" containingflili) methyleneigrctiips Both thepolyester's and advantages and certain disadvantages; The poly,est er's possess fhigh melting 'points: and exceptional strength characteristics, but the 'terephthalates are ,highlyyinsoluble and very difiicult to dye; Anattempted modification in order to achieve the desirable properties of both the poly esters and the polyarnides was'disclosed by Carothers and involved coreactinga dicarboxylic-acid, agl ycol and avdiamine to form a *polyester amidef? In suchipol yester-amides, however, there are the competingreactions of polyester formation and polyamide formation, and the properties of the resultingproducts were disappointing.

An attempt to improve the properties of the polyesteramides was shown wherean-excessof by Brubaker et al. US. 2,224,037

formation. *Even inthis case, however; themelting polymers was very low and the poly:

I ter'ephthalate polyesters'inutility.

' In the preparation of herent? viscositytoachieve ucts with good physical characteristics. forming stage laterally or both, and usual"tensile strength; flexibility; physical; properties. lt has ence of amino groups or elongation land-1 similar williamsfiochester, p

thetiolyanudesuposs s vcerrtam' ester was usedto try to overcome the tendency for polyamide' formation in preference topolyester points of the mixed 5 ester-amides 'knownh'eretdforeihave not approachedithe 4 condensation polymers, it is de- 'sirable to -be able to formpolymers having asufli cient infilm and fiber-forming' prodwhe thstfib is reached, -'the -polyrners are, capable-of, by-being-stretchcd either longitudinally or the oriented polymers possess u n-' been'* recognized that v the ag dc linkages in condensation lubi i y 1y ab 1 y a d t e propertiessuchias'softening 7 tempe'rature havez sufieredsuchga d c ne'fthat olyesterv amideshave nocachievedwidespreaclcomrne' Patented Feb. 16, 1960 results in'products with undesirable color. Consequently, it has been; desirable todiscover some method of-,forming polymers which retain the desirable properties of polyesters, such asjthe polyethylene terephthalate, esters, but which also include amide linkages effective ;to improve idyeability, -processability, moisture absorption and the -like'.-- to 4 ItQis accordingly-anobject,ofithi invention to provide "new and improved ghighly polymeric --,-l i near'- polyesters containing."amideglinkages efle'cti vove Qmeg-thedis- Eadvantagesinherent f in r-prior polyesters gw hout 'sacrifieingthe desirable: properties:characteristic of polyesters, particularly of the terephthalate type. 1 1 I; ;It iszianother object of the invention to prep re hitherto unknown homogeneous polyesters possessing'regularly' recurring polyester-amide structural unitsbut free-{ofthe disadvantages usually associated with'polyester-amides,

@IA zifurther object; of "the, invention is to employ-mew monomeric 'bifunctional 'dicarb oxylic compounds contain,-

1 ing amide linkages; equal in1number toithe ester groups for polyesterzformation withoneor more allgylene lyeols,

vand preferably;polymethylenel1g1ycols. J a

Anotlierv object;of thez invention, to, .tprovid a new class fof'thighly polymeric, linear condensation lym ers 5 having physical properties at leastas good asany polyr-vmers known to theart, and possessing a combination of fprdbrtijes not possible with polymers "known heretofore.-

Another object of the invention is to provide polymeric materialshaving unusualutility inithe: manufacture of shaped articlesf suchas fibers; films, 'she'etingandthel-ikc,

and capable'of being oriented to givei unusualjstreng'th,

oii'gl ness, =fiexibility,' 'and elasticity 'zcombined zwith: rimvedfdy'e'ability,fsolubility, pr'o'cessability:andimoisture bsorptio withoutobjectionable"eoloriformationand the sacrifieet5fs6fte in temperature;

'Anot'herobjectfoftheinvention is to provide p'olym'eric 'jrnatei-ials assessrg unusual utility as film base materials orth'e manufacture of either black and .white. of. color I photog'raphic'film of exceptional strength,'wear resistance 40 and dimensionalstabilitys] :1 j: 1 1:

' Other objects" will *be apparent trom the -description and claims' which follow.-

I: a i 3 $2, These and other objects are attainedzby means OfzthiS invention wherein highly polymeric linear .condensation polymers" having a regular structure composed of "a succession'bf recurring structural units of th'e -forrnulas 2' reacting at lea ne alkylene gglycol .ofSZfli) carbon atoms, j preferably a? polymethylene glycol; .with at least'on'e ester'ofa dicarbo rylicacid of-the formula,

obtained y -r niac'rdane i i the", arboxylicacid of the form P Y rm wherebya'cornpletely;regulate ure is obtained; me here 'are fnozcompetinggpolyeste and polyamidefireactionsduring the olymerizatio merges I sstead, the polymerization reaction 'is a polyester reactionare readily made-in viscosities sufficient-for formation-f fibers having the improved properties characteristic of oriented polymers, and-can be made at viscosities of 0.7-1.2 and preferably about 0.9 with no difiiculty. -'The "'r'n elting points of the polymers embodying the invention are-unexpectedlyhigh, usually being in'excess o'f 200 C. with inherent "viscosities' 'of 0.8' or'hi'g'her, melting p0int's of-2 40270 C. commonlybeing obtained. This melting point ran-ge compares closely to that fif conventional terephthalate polyesters and is inma'rked contrast to the melting points of 80-'l50 C.-which areco'mmon v'vithpreviously knownp'olyeste'r amides preparedlbyv conve'ntional' methods. The polymers of the invention also poss'es's'great strength,"fiexibility and wear resistancetcomparable-to the best unmodified polyesters, and in addition contain regularly recurring amide linkages which, without -obje'c'tidnable color 'fo'rmation, are effective to improve,

dy'eabilit'y, processability, and' moisture absorption.

In practicing the invention, the esters'of the dicarboxylic acid, NJN -bis (p-carboxybenzoyl)alkylene diamine of '-'-the*formula Compound I can-be prepared in any, manner. whichwill give the mates'r'ial in monomeric form. The nature of theester group -is-not' usually'of great significance. since it is split oif'in the initialtester-interchange reaction with theglycol when theilglycol Foster 'is formed 'in the initial stages ofthe reaction. Thus, for example, the phenyl'estercan be used,

' lalthotigh the'alkyl esters are preferred for convenience in"removing the monohydric alcohol liberated in the initial ester-interchange stage of the process. Of the alkyl amine, preferably a polymethylene diamine, with two.

.molarproportions of a p-carbalkoxy benzoyl chloride "under controlled'conditions whereupon the desired -'rnonomer is obtained in nearly quantitative yield. The'diamine employed can be any of the alkylene diarnines 'eontaining'2-10 carbon'atoms; and, if desired, monomeric mixtures can be prepared by .employing two or more diamineswhich is v sornetirnes idesirable.:when a po'lymer'having particular properties is desired. ,Of the diar'rlines, either straight or branched chain alkylene diamines canbe used, with the polymethylene diamines typified by thylenediarnine, trimethylene'diamine, tetrarnethylene diarnine, pentamethylene diamine, hexamethylenediamine, heptamethylene diamine, octamethylene diamine, rionanrethylene dia'mine and decamethylene diamine being preferred.

As-indicated hereinabove, the nature of the ester: groups drrthe monomer do not affect the-course of thecondensationprocess-and the diamine or diamines can "herearmed with p-carbophenoxy benzoyl chloride, p-carboin'thoxy ibenzoyl lchloride, .p-carboethoxy-ibenzoyl, chlo- I ride, *p car bopropoxy benzoyl J chloride, ,p-carboiso'propopxy beneoyl chloride, .p-carbohutoxy. benzoyl ch loride, p-carboisobutoxy benzoyl chloride or similar pcarbal kox'y benzoyl chlorides ;as desired to form the .dicarboxylic monomer. The dicarboxylic monomers and their preparation is disclosed and claimed in the copending application of Williams and Laakso, Serial No. 504,105, filed concurrently herewith. The preparation of typical dicarboxylate monomers used in practicing theinvention is illustrated in the ifollowing' .examples,althoughf it will be understood that'o ther monomers as defined-therein can be used in practicing theinventio'n regardless of the method of preparation of such dicarboxylate monomers.

amli e 1 -Undcr 'essentially dry conditions,.20,parts by weight (0.3 molar equivalent) of-ethylene diarnine was dissolved in 250 parts by volume of dry pyridine and the solution chilled to 0 C. With efiicient-stirring, .1275 parts by weight (0.6 molar equivalent) of p-carbethoxybenzoyl chloride was :added slowly to the solution at-L3. rate whereby the temperature was maintained between 0* and 10 C. Stirring was-continued for 15 minutes,-and

hol, pure white, N,N-bis(p-carbethoxybenzoyl)ethylene diamine .melting at 124515-246 C. wascob-tainedzin a yield of of theoretical.

Analysis-Calculated for C H O N C, -.64.-2; .H,

C, 64.5;:H,26.1;.1N, 7.3.

TEx a'mple '2 (0.3 molar equivalent) of hexamethylcne diamine was dis- :solved in *500 parts by volume of dry pyridine and chilled to 0C. With efficient'stirringu 1275 parts-by'weight (0.6 molar equivalent) of p-carbethoxybenzoyl-chlor de was added slowly to .the solution whileimaintaining the solution temperature vat 0" to -10 C. Stirring was continued for 1.5 minutes whereupon-the reactionmixture 'wasipoured 'into'ice water. The light cream colored solid which precipitated was :filtered by suction andrecrystal- 'lized from ethyl alcohol'togive. pure white N,N bis(pcarbethoxybenzoyl)hexamethylene diamine melting at 207 208 C., in a yield of 88.8% of theoretical.

Amzlysis.-Calculatedv for C H O N C, 66.7;H, 6.8; N, 5.9. Found: C,67.0; H, 7.l; .N, 5.9.

Example :3

:A'solutiono'f 801g. (2 moles) .of;sodium hydroxide in 300.ml.of water was'added,with stirringto a solution of 161g. (1 mole) of tetramethylene diamine hydrochloride in 500 ml. of water. 'To'the resulting solution, 1 literlof benzene was added, followed by.l98,.5 g. (1 mole) .o'fpcarbomethoxybenzoyl chloride which was added-all at once with'efiicient stirring. After 5 minutes, rnl. (.1 mole) of sodium hydroxide *solutionwas addedrapidly. Thereafter at 15 minute :intervalsgp-carbomethoxy :benzoyl chloride and sodium hydro'xidesolution were added successively until an additional 200g. .of'the acid chloride and 'an additional 150 .ml. :of caustic solution had been added. When addition was? completed, the react on mixture was-stirred for onehour and thentpoured into col d water-to precipitate the product. The white product was' filt'ered, washed withwatentdried,recrystallized from I dimethyl formamideywa'shed with alcohol: and dried to give white crystalline'N,N-bis(p-carbomethoxy benzoyl-)- 'tetramethylene diamine melting at 25-5-'-;256'-'C.zin'a yield mole) .oflp-carbomethdxy fben'zoyl' chloride'was -added dropwise to a well-stirred'solutiondf 58*g.- (0; mole) 'of hexamethylene Zdiamine in 1000 ml. o'f-fdry pyrrdme. IlEhc 'em aaereemmartm metastabelow invention can be 5 group or aphenyl group as desil egh. p a Thesecond stage of hejpr0ci s.'erribqdyin the 5o C. during the addition. i reaction, mixture'was stirredfor one hour, po'ured intoicc water, and the cream colored-precipitate was filtered ;outand recrystallized from alcohol. Theyield of pure .white N,N'-bis(-p-carbomethoxy benzoyl) hexamethylenejdiaminewas 63% of theoretical. I

. Analysis.--Calculated.'for C,.,H,,0,N,= C,, 65.4; H, 6.4; N, 6.4. Found:.C, 65.8; H, 6.4; N, 6.2.

The dicarboxylic monomers useful in practicing the invention can thus be methyl, ethyl, propyl, isopropyl,

- but'yl, isobutyl. or other die'sters, of such dicarboxylic acids as N,N'-bis(p-carboxybenzoyl)fethylene,.diamine; N.N'-. bis(p-carboxybenzoyl)trimethylene diamine, N,N 'l-bis(pcarboxybenzoyl)tetramethylene'".diamine, .N,N'-bis (p-car-' boxybenzoyl) pentamethylene .diamine, N,N'-bis(p-car- ,boxybenzoyl)hexamethylene boxybenzoyl)heptamethylene diamine, N,N'-bis(p,-car- :boxybenzoyl)ocfamethylenediamine,,N,N? bis(pecarboxydiamine, N,N-bis(p-ca17- benzoyl) nonamethylene diamine, and N;N"-1bis( p-carboxybenzoyl)decamethylene diamine; "and: suchampnomers can be employed singly or'incombinationsroftwo or more of these or similardicarboxylatetmonornersas deably being employed predominantly. a i t v L The glycols which are desirably employed for reaction with the dicarboxylate monomerj-are'the :polyme'thylene: 1

glycols'such as ethylene glycol,trimethyleneglycol, tetramet hyleneglycol, pentamethylene glycol, hexamethylene glycol, hep'tamethylene glycol, octamethylene glycol; non- .amethyle'ne glycol and decarnethylene. g ycol T which can {be employed single or; in mixtures of two or more, al- 1 though other alkylene glycols I suchas '2,2 dimeth'yl-propanediol-1,3 and the like can be used'alone or preferably together with a glycol; The initial stage of the process embodying the illustrated graphically asffollows:

, Glycol Diearhoxylate monomer lower alkyl group lbut' canlbmhydrogenila l kyl tion gcan [be illustrated graphically asf ollcwst 5 Unckr ordinary? reaction conditions there is very little degradationofthe dicarboxylate monomer and conse' quently the polymeric product consists predominantly of regularly recurring structural units of the formula joined directly together in, a linearpol ymer chain. L

is in contrast tothe random structure obtained, by con- .co'mitant coreaction of a glycol, a dibasic acidg'andadiwherein are wmveing vc x s rra anama reactions, 7 i

'In carrying out the process embodying,tlie'iifintion, one molar proportionof; the dicarbdxylate Lmondmeris reacted with at least two-molar, proportions of ,glycol. Breferably an excessof glycol, is employedfilhe initial ester-interchangeisreadily efiected lay-heating the mixture;

of glycolcompdnent; and dicarboxylate;monomer component in the presence of; an ester-interchange catalyst and at a; temperature ahoye the melting point of the reactants.

vThe initial; stage of the reaction is ,usually carried, out I at atmospheric pressure and atemperature of 1001 300" C, andpreferably 200 %30(l C. for best results, although lowerpr.higher temperatures canfbe employedin some "cases. During the course'o 'f the ester-interchanges in.

initial stage of the process, monohydric alcohol 1 is liberatedfcorresponding to the nature of the ester gro ps 011 the. dicarboxylate monomer-or water. when the free dic 'arboxylic'acid is used. For best results, the watero'r alcohol, is :removed from ;the reaction zone ,as it, is ..liberated in order to, shift the reaction equilibriumto; optimum I no-n-ogil-nn m nn-il v Glyiea l est erg! dleertioxylate monomer i this'initial stage R land'R" representialkylene groupsofZ-IO carbon atoms, andRf is preferably a predominant amount of -polymethylene 5' formation of the glycol ester, 10f the .diFii 'bgxYlate mono'rner. As has-b'e'en-indicateithedicarboxylatemonomer is desirably employed in the f lm! .aJQW l' ky jd fii for :easeLof removal aofi the l-liberated alcohol,- na ging, however, jhigher alkylior phenyl esters 1 can he used, as

".well jas the free dicarboxylicacid or an ester-forming "derivative thereof suchsas a salt, halide oramine.

change catalyst, a largenumber of suph catalystsbeing known to' the, art. Typical ester-interchange catalysts which canbe employed include the metaLhydrides such ascalcium hydride, lithium hydride,, sodium hydride, ortthe like; metal oxides 'such: 'as antimony .trioxide,

.-.litharge, cerium oxide, germanium, oxide and; .thelikef' double metal catalysts such as lithium 'aluminum stearate, max m aluminum acetate and similar catalysts'con- 't'aining an alkali orjalkal ine earthmetal and anarnphotal, alcoholates of oneflor more of such metalsf'as aluminum' iinc, 'and the like falkalinef reacting .Thelprocess is facilitated by use' of an ester-interpotassium, lithium, calcium,-titanium,;tinfmag has borates and .ca rbonatesfof the alkali metals,

*fiber forming "stage. 'byfirstobtaininga low viscosity polymerin powder form, "and then-continuing 'tlie'polymer build-up in powder form under'vacuum, or'by continuing the heating after the: initial stage underreduc'e'd pressure whereby the poly- "spasms free metals sneh as-sodium, potassium, lithium, *caleium,

cobalt, tin, germanium, cerium, magnesium, tin, lead,

antimony and-the like as wellas salts of theseand similar metalsan'd *other well known ester-interchange catalysts such'tas zirconium compounds and the like. Particularly goodfresults are obtained with the titanium compounds such as titanium butoxide, sodium hydrogen titanium ethoxide butoxide and the like, preferably together with water as "a co-catalyst for low color formation. The catalyst -or catalyst .mixture is preferably employed in a concentration of'at least 0.001% by weight b-ased on the weight of'reactantswith-amounts of 0.001% to 0.05%

by weight being preferred. Larger amounts of catalyst 'canalso be-usedalthough such larger amountsnsually 'are'not necessary for optimum results.

The initial stage of the reaction is usuallycomplete Polymerization of the glythe'desired 'degree'by continuing 'the heating under reduced pressure at least until the polymer reaches the The polymerization can 'be efiected nier remains molten until the desired molecular weight and inherent viscosity'is achieved.

The polymers embodying the invention are polymer- 'ized until a fiber-forming stage is achieved, i.e.-unti1 ya rod dipped-into the -melt will pull -aflfilamentwhen drawn from the 'melt.*' Usually for optimum results, thepolymerization is-carried out until an inherent'vis- "ciisity of at least 0.8 is attained with viscosities or "C. The preferred polymer compositions are those'havingmelting points in the range of about 240-280 C.,

"since the, polymers melting above about 280 C. 1 are diflicnlt to extrude and process in commercial practice. Asjhasbeen indicated, any one or more of the'alkylene glycol's containing 2-10 carbon atoms can be condensed with "anyone or --more of the dicar'boxylatemonomers 'as'de'finedherein. The resulting polymers can be:used

alone or in blends of two or more of such polymers, or blends of such polymers with other polymeric materials such as polyesters, polyamides, copolyesters,;polyesteramides and the like. In some cases, it is also desirable to modify the polymers by coreacting anotherdicarboxylic acid (preferably in ester form) with the glycol and dicarboxylate monomer, such other dicarboxylic acids being typified by aromatic dibasic acids such "as terephthalic acid, isophthalic acid, 4,4'-sulfonyl dibenzoic acid and the like or aliphatic dibasic acids such as adipic acid, sebacic acid, azelaic acid and the like. The polymers of the invention can be quenched following polymerization by cooling to. a temperature below the. minimum crystallization temperature, about 80 C. The polymerization proceeds rapidly and ordinarilythe fiber-forming stage :is reached within ";30minutes, although the time necessary for polymerizausually below .tion -;will vary dependingaupon the heating temperature, kind and amount of catalyst and similar variable'factors. The polymerization is facilitated by removal from the reaction zone of the glycol liberated during the poly-v merization.

'lhe polymers thereby robtained ean me fextnr'ded from the melt =to 'form filaments or sheets as :desired. The resulting' shaped articles areithen oriented by being stretched 'either ilaterall'y or longitudinally :or *both whereby fa marked increase in physical properties is obtained. "The degree of stretching will vary somewhat dependingznupon the polymer composition and .the properties desired, -.but sheets, films, fibers, =etc. 'a re.=usually :stretched 600.% of their' original extruded dimension for :best results. The shapedarticles are usually cold drawn, ize. :drawn at]; temperature between the :second JOl'deI' transition "temperature sand the 1minimum:::*c rystallization temperature-of the polymer; although, unlikerthe usual :zpoly- -esters, the=polymersembodyingthezinvention can be ori- 'ented by drawing Lat :temperaturesrof as :much as 50 above the minimum-i'crystallizationtemperaturein some 'The'rfibersgfilms, =sheets, .-etc. which have been drawn are "characterized by exceptional physical and mechanical properties, including istrength, flexibility, wear resist- :ancerand thezlike; comparable to terephthalate, polymer-s. In additiomthe polymers of the. invention have unusually high heat distortion temperatures which are often as "muchas 40-.C.:1'above itherordinary heat distortion temperature iof terephthalate ipolyesters which have been :oriented 'rbut 'JIOtiTCifiXCd. Thepolymersiof the inven- 'tion thuszpossess therexeellentmeltingpoint-and physical -=characteristics 10f. the "best polyesters :known; heretofore highasw fl gramsper-d'eniercan be readily obtained,

combined with 3 good dyeability and moisture absorption whichrusually are sacrificed in conventionalvpolyesters. The polymers/also .possessrexcellent utility in photograph ic applications1asgfor example 'for useas film-base for carrying photosensitive silver'halide emulsions in blackand-white 'or- .co lor film. The unusually high heat distortiontemperaturealso makes these polymers unique for applications where dimensional. stabilityagainst .thermal distortion is .a seriousproblem. V

As has been indicated, any of the polymers consisting essentially of recurring structural units of the formula ii i i ii {om-04:00 m une-O0} whereinR is an.alkylene group of 2-10 carbon atoms and R is a polymethylene group containing 2-10 methylene radicals, are within the scope of the invention.

" For manufacture of films and fibers, 'it is usually desirable to employ a polymer wherein the total number of carbon atoms in'R and R together is at least 10 in at least half of the recurring structural units. For best results and optimumcombination of properties, the combined number of carbon atoms-in R andR" is desirably at-least '12 in an at least one quarter of'the recurring structural units. The-polymers which have shown particular utility v,are those wherein "a substantial amount 1e t I 0 ,I 0 {wswm tm(est-mugs} desired degreeaof crystallization resultsfltsln dhe case of film tobe'used-for photographic applications wherepit; is r i is desirably extruded from the -melt either onto a pasting uroll or-betweenpairedrolls and then drawn bothlongitu'dinally and laterally, either coneomitantly -or-suu i cessively, to fromv 100-600.%- jof its original; dimensions in order to orient the molecules. Thereafter,tthe ori- V -'ented .filn'ror sheetis desirably heated atla temperature .abovetthe minimum crystallization temperature :until the desirable to coat: the .film with photosensitive silver halide emulsions or'othercoating layers, thefil'm can be coated vwith. a subbingimaterial, such as a-resin.orjcopolymer sub before the orientation or; between the; drafting steps "orbefo're the heat-:treatmentfollowingflorientation. 1; In sorne cases, particularly withmodified polyester2-subs of good solubility, it ismore convenient to sub the ori- :ented and crystallized film after the film processing has -been completed. The subbed film can then .besupplied with the usua tion backing, etc

graphic practice. 3 .1 t In the manufacture of fibers, ithe moltenfpolymergis extruded through a" spinneret; and quenched; Theresulting fiber is then drafted 60-'- 600%; and heatt'reated for crystallization.- The resulting fibcrs :have 'hot bar 'sticlting temperatures above 200 C. injmost casesjcom- "-bin'ed with strength of the order o f-6-q-8;gr'ams perdenier, excellent dye affinity for. most te'xtilez dyesjand moisture absorption characteristics which make =the fibers resemble natural fibers more than-is generally. thecasemyyith synthetic polyester fibers. esters"containi ng amino groups, very tion'is observed and textiles prepared from'fibers. cmbodying the invention can be dyed to deep shades or with pastel dyes or fleeting tints as desired.. Consequently, the polymers of theinve'ntion show unique "versatility among the synthetic condensation polymers since they combine the desirable characteristics'of both the polyesters'andthe polyamides without the disad- -vantages of either type.

The improved results obtained in accordance with the invention appear 'to resul "structure which is. obtained-by condensing the 'glycol f =N;N-bis(pcarboxybenzoyl-h in accordance with wellknown photofmo'nomeric ester h polymethylene dia'mine This is int: which are obtained by a' variety o the other possible combi- 1 o thepresent invention .un first reacting a terephtha diamine and reacting reacting the terephthalat d'er usual" practice" include reacting the resulting product with; the'rpolymethylenel diamine; or forming prepolyrners teririinating inamino l photosensitive emulsion layers, anti-hala- In contrast to the nsuai little color;;f

t from the unusually; regular h ontrast tothe results n i methodsr involving 1 competingreactions having dif ierent' rate constants such as ester-ester interchange, esfi'r glycol interchange, ,aminee-glycoli interchange. :The 11y proceeds most rapidly a p vme a :Ihu j" actions, polyamide is{ u,s u-

in. order ariousfheter'ogeneo'us'polyester #l -"antide; processes which do not giveresults comparable;

late ester with a polymethylene the l product} .with a glycol; first eester and the glycol. and then; v

groups for reaction with ester. groups or terminating in ester groups forreactionwithdiol or amine groups. .In'the jusual case, it is not feasible to stop'fsuchlreactiofis fat the desired monomeric dica'rboxylatefstage necessary 10 to produce the polyrner sjof this invention, and varying ,the ortler v of addition of the various components does 'tionfa'r'e mostreadilyiillustrated bycompariso Qth tlie '1. heatingfluiid the melt 'rose w i ht P m W results obtained by; 'esses; "For example, under1'comparable j conditionsyt'he" heterogeneous,polyester-amidefrom heit'amethylene an ne; ter'ephthalate ester;i'anayhexanetnenioi has, a ,meItingjpoint'of i ZII" C. aridanfinherent viscosityof I 0.60 ereas the polymer of this inventionprepared from i1eXane-v1,6 -diol and the monomeric ester of 'N,N bis (p- I carboxybenzoyl)hexamethylene"diamine" has a melting point of 270 and'an inherent viscosity big-1.16. In the 25 case of this particular type of polymer, it is usually necessary toachievean inherent viscosity. of the order of. 0.8 in order to obtain satisfactory fiber-forming characteris w tics. andlgood physical properties. Thefollo'wir igiEx- .-a r nples 5-9 illustrate the results obtained by nnate. geneousprocessesdn contrast to the remainder offthe examples illustrating the. preparation .ofthe homogeneous I Po me qf hi i ve io r v f 4 e 4 V Example'5 ,H ii h ei t j -6r -f(0 1 9 )'t di minefai 149.61g. (Q. 2"'in ole) ,of 'diinet l 'terephtha'late l wa$- t?= i 1nd fh t o z w afic fi m n-n t tites, a 'violentie'volution of methanol occurred. and the imelt'rapidly' became viscous. Io 'the'meltigwas added 50;; g; (0.421 mole) ,of hexaneelyo-diolf and" 0.5 ml.- 'of V catalyst.solutiontfiiepared byfadding O.1f"ml. oftitaniu'm' hutoxide to a 'solutio' of 0,1 g'. of sodiumin5'0, mlfbf' i resulting nixturewas heated-for" F n ospheric pressure followed f F nn at 270.? h osity a i l w vii an a: ve y? 'q' molciilfir as obtained containing 315% v nitrogen. A "YExample 1' .'I 1:9 1 5:

A mixture of 39 g. (0.2 mole) ofdimethylterephthalate, g. (0.42 mo1e) '.0f hexane-1,6-diol, 11.6 g. (0.1:mole of hexamethylene diamine and 02 ml. of the catalyst solution d'escribedin the preceding example washeated at .175-250 CQ f or 30 minutes antl atj z5t) C.I,forl 20 minutes. melt was then' heatednnder I 5;" C. ff orf 10 miuutes,"but th'eFpoIYmer ethane' 's'ol det'rminav,v iwn a 'nseluble in phenolrtetrachloro i t vsa sm v -fir I1 (5' fofii) minutes; To the melt'was w tli usual practice.

spasms I1 mole) of hexamethylene diamine, and the mixture was stirred under vacuum for 20 minutes at 275 C. The product was of low molecular weight and had an inherent viscosity of only 0.24. i

Example 9 ..A. 9.7. g.portion (0.02 mole) of 1,6.-bis(p.-carbocthoxy- ,phenyl.carbonyloxy)hexane was melted under an atmosphereof dry: nitrogen at 240 C. .To the melt was added 11.2 .g. (0.01 mole) ofhexamethylene diamin'e, and the temperature was raised to275 C. over a 20 minute period. To the mixture was .added 1'.9 g. (0.01 mole) V of dimethyl terephthalatesand 2.4, g. (0.02 mole) of hexane-e-diol. .After. heating the mixture at 275 C.

and 1 .pressurefor. 20minutes, a polymer was .Qbtainedhavingan. inherent viscosity of'0.6 and a meltius'point o'f.,210.;C.

.Ifhe heterogeneouspolymers prepared ,as described in .-the..preceding"Examples '5-9 have little utility as'film and fiberforming materials as compared to the homogeneous polymersembodying this invention, as described in the ,follcwing examples, which are among the best materials known for fiber andfilm applications.

I Example; ".To ;;.a mixture. of 8.2parts by weight o'fN-,N-bls(p.- .earbethoxybenzoyl)ethylene diarnine and '11 parts by weight of decane-Ll'O-idiol at 250"C. .under'nitrogen was addedv 01 part by volume of a catalyst solution prepared byv the addition of 0.1 part by volume of titanium butoxide to a'solution of 0.1 part by weight of sodium in 50 parts by volume of absolute ethanol. The temperature of the reaction mixture-was held at 240270 C.

' for 10. minutes during which time ester-interchange occurred with formation ofa' glycol ester and liberation of ethanol. The ethanol was removed from'the reaction ,zone, as formed by means of a water aspirator. Thereafter, the reaction mixture was heated at 270 C.. and

" 0.1-mm. Hg pressure for 15. minutes; 'The resulting polymer had an inherent viscosity of 071 and a melting point of 274 C. .It could be readily extruded from the melt into films, sheets or fiberswhich were quenched,

drafted about 400% and heat treated 'at' about 170 C.

Theresulting oriented articles were extremely strong and flexible, possessed excellent dye affinity and exhibited.

unusual thermal. dimensional stability. 7

The polymers of the invention are'also useful in making tubing, molded articles, sheeting for packaging, coating-m t r als a d s- Example'II mixture of '9'.4 parts by weight of N,N'-bis(car- =bethoxybenzoyl)hexamethylene diamine and 10 'parts by weight vof..pentane-l,5 diol'was melted at.'250' under ;a .-.drynitrogen-stream. Catalyst was added as in 'the preceding example, and the reaction mixture was heated or;.16.,minutesfat 240- -"270 C..w ith removal of the liberated alcohol to effect ester-interchange; Thereafter, the reaction mixture was heated at 270"- C. and 0.1 mm. Hg pressure for 8 minuteswith continuous removal of .glycol liberated in-the-condensation. The resulting poly- .-mer,,hadan'-inherent vviscusity of0.97 "and a melting point of 255. C The polymerwas readily extruded from the melt into films and fibers. After} drafting and heat treat- .;-.ing.withou trelaxation, fibers having strength of theorder .of 6'-8.- gwper denier and excellent dyeability 'areobtained. The moisture absorption, isof the order 'ofl% forfthis .;aud;.many. similar: polymers which 1 makes them particularly adapted for textile applicati ns .Wherein fthe highly hydrophobic character of the usual polyesters -is 'a disadvantage.

1.. b msraahic- {Ina s .9141 be. t erartd inaqse daas The polymer .wasof particular utility for" filmbase in the-manufacturea of photographic film, and- .fcould besubbed with resinsubs, such as the'vinylidene K chlpus e rare -m re. wher byj usua we ken -w or Example 12 A mixture of 9.4 parts by weight of N,N'-bis(p-carbethoxybenzoyl)hexamethylene 'diamine and 7.1 parts .by weight of hexane-1,6-diol was melted at 250 C. under nitrogen. After addition of ester-interchange catalys't as described, the reaction mixture was heated at 245-270" C. 'for5 minutes with removal of the liberatedalcoholv:

Thereafter, the mixture was polymerized byheatingfor 14 minutes at 270 C. and 0.1 mm. Hg pressure. The

polymers obtained had an inherent viscosity of- 0.96 and 'a melting point of 265C. Althoughithis polymer could be -spun into fibers of excellent mechanical and physical properties; it was of particular utility. for filmbase in photographic applications.

In black-and-'white. or. color photographic-film, the oriented polymer shows excellent wear'resistance, strength and resistance to flex cracking.

Its heatdistortion temperature is about 180 C. which is highly desirable for'thermal dimensional. stability.

Once oriented, it does not readily lose its orientation,

and it exhibits orientation even when drawn atv temperatures well above its' minimum crystallization temperature. Its melting point makes melt extrusion practical on :-a commercial scale, withouthaving an .objectionably' low softening temperature. Theamide linkages in the monomer employed as well as in the other monomers 1cm bodying the invention are very-"stable under-the .polymerization conditions so'that the content of free amine is very low in the polymers. Consequently,.the problem of objectionable color .formationcommon to polyesteramide processes known heretofore is largely obviated in. the process of this invention;

As can be seen from the examples, the polymerization in accordance with this invention proceeds rapidly tothe fiber forming stage which is a definite advantage fro m the standpoint of commercial practice. The easeof-ester- "interchange and condensation makes the manufacture of a polymer possible by continuous as Well as batch processes.

cated, it :is usually desirable to employ a substantial amount ofglycol anddicarboxylate monomer" wherein the numberof carbon atoms in the polymethylenelportions of these. two materials totals atleast :10 ,and preferably at least 11. The long chain glycols, such as decane-l,.l0vdiol, are relatively scarce and expensive. howeverfand rather than prepare a simple polymer of 'decane- 1,-l0-diol and N,N-bis(p-carbalkoxybenzoyl)ethylene diamineas describedv in'Example 10, it ispreferableto mploy a .mixture of dicarboxylate mq or sglycgls .-;asshown;i h f ll i gxamplg i 1 v Exampleilfi' A mixture of 23.4 g. ..(0.05 m0le) or uisr-uisr aru .ethoxybenzoyl)hexamethylene. Qdiamine, 20.6 g. (0.05 l f :N,N' -.bis(p f carbethoxybenzoyl)ethylene diamin e,"f40 g. 'of hexane-l,6 diol and 0.5 ml. of catalyst solution (prepared by dissolving 0.2g. ofsodium'and 3.0 ml. of titanium butoxide in suflicient absolute. ethanol :to givefia finalqvo'lume of '100 ml.) was heated lat "250-270C. for 20 minutes to effect ester-interchange.

The reaction-mixture was then heated for ZO rn'inutes at 27 5 C. and 0.3mm. Hg pressure tOetfectpQIymeriZation.' The "resulting polymer had; an. inherent viscosity of 0.84, and a melting point of 262 C. Filmsjand fibers' of excellent Phy ical characteristics were readily extruded Lfromja; mfelt of, this polyn er, fwas' par- "eularly,usatuhfuruwrasriil,

are

v i. VQ FWK 'Z some caseswit is desirahle:to.employ;a mixture-of -glycols, particularly fromthe 1 economic standpoint. For

assisted iexample;a:.chargeEzconsisting ofi46.8. g. (0.1 1mole) of I-l,N'-bis(p-carbethoxybenzoyl)hexamethylene diamine,

17.7 g. (0.15 mole) of hexane-1,6-diol, 13.5 g. (0.15 mole) of butane-1,4-diol and 0.5 .ml. oicatalyst solu- .tion (prepared by ,dissolving.0.2-g.'of sodium-and 3,0 ml. of titanium butoxide in sufficient absolute ethanol.-

.to. make 100 ml of solutionl was subjected to esters interchange for 20' minute'sat 240-275" C, Polymerization was then effect dbyihatingfthe meltfor"20minutes at 275 C. and 0. l' mimj Hg pressures ',The resulting mum havingau inherent vis osity of 1 109 andavmeltture' of films and fibersJ-as the'other'polym'ers' embodying the invention. i r p Example v 7 In the-preceding'example, equalmolar proporti the ,tettamethylene glyeo l and. the hexamethylene glycol fjjwere' employed; but other 'proportions can be used with jequallygadvanta'geous res'ul Thus, a charge oi t6'.8 g.

icatalyst solution described ingthe pi'eceding example was heated fol-'20 minutes at245*275 ='C-. to effect esterinterchange. The melt was then heatedfor' 20*rnin'utes at 275" C. and 0.1 mm. Hg pressure. The resulting polyrner hadv an inherent viscosity of 1.01 and melting point z 9 C. a 1 ,v

' Example 16 abilitybf the polymers result non use o'ftitaniurn' -butoxide' catalyst instead of other "'well known ester-in'ter- "change'catalystssuch as sodiu'r'n hydrogen titaniurniethoxidebutoxide catalyst. A catalyst solutionwasprea pared by. dissolving 3" 'g. of-" f ijeshly dist'ill'ed titanium 40 fibutoxidein suificient absolute alcohol to make 100' ml. o'fsolution.* A-chai-ge of' 46".8' g. (0.lmole) of N,-N'- bis(p-carbethoxyben zoyl)hexamethylene diamine, 35;4' g.

(0.3 mole) of hexane-lgo-dio'l and 0.5 ml. of'the catans of ,ofqtitanium butoxide and water. gthe-process ,Was carried out at 2 75? C. and.0.1.v".0,5 mm.

problems in e aration ana' handling because at pressure for 20 minutesn; The polymerlobtainedhad an inherent viscosityof 1.20.and a melting p of 263. C. and wasnearlypure whiteincolor I u I I 0.11 "mole, r 'Ngn -b (p-ca'rbomethoxyminute; or;

"fi t'rbges-ogz g, r sodium a for freshly distilled. titanium but'oxide' in sufiicient a oholto' make 100 ml.

Particularly g od results fidmj'the standpoint of nuencht;

lyst solution was heated for 20 minutes at 245,-275p C.,

followed-by 20 minutes heating at 275", C. and 0.1 Hg pressure. The polymer-obtained had an inherent viscosity of 1.21 and a melting point of 264' C. It ;;quenched readily ,andwas of particular utility, for film haserfor photographic film. g 1

The nature of the esterligroup, on'the dicarboxylate .monomerjdoes not affect the course of the polymerization since this grouprsplits' blf during the .estereinterchange occurring in the first stage {of thefprocess. Because of its unusual solubility characteristics, the isobutyl ester is easier to prepare and gives excellent results in the condensation. A 'chargeot'52.5 g.;(0. l mole)"of N,N- b is (pcarboisobutoxybnz'oy1)hexamethylene diamine, 35.4 .g. (0.3 mole) of hexane-1,6-diol and 0.5 ml. of the cata- I ly'st 1 solution described the preceding examplewas j heaited'fforf'lolninutes at- 245'-2 75 C.'gfollowed'iby l5 ini'nutes t p6lyn'ter *obtainedhadanZinherent viscbsity or 1.06 a v melting point of 264 C. and quenched' readily;.-.

j E-EWR'H? amount;oi catalyst employedcan be varied with-' affecting the course of the reaction.

The

-Thus; the" process asQrepeated-using double the amount of catalyst The meltingipoint of-264 --C. andquenched readily.'- l

v Example 18 Or in y. of t e estcr igtgrgh s c ysts yrsdescribed in the -p'rece'ding example 275 Q'Jand 0.12 mmsHg pressure?" The v Q2, prepolymer was preparedand' powdered insthe preceding example. The prepolymer waslthen reheated lynierfobtained had a an inherent viscosityof 1.13; a r

l 6-diol'and 015. ml. ofsodiu flhydrog'en titanium ethxide butox'ide solution ,(pr 'ep ared by dissolving under .ofi solution) was heated for minute's at 245:275 C.

for 20 minutes undeunitrog'emi and then heated for 15 ',1niinutes ,at'275" C. and 0.1-0.5 mm. pressure. 'Thep'olymer obtained 'had ah inherent viscosity of 0. 69 and a A mixtureot Q'l,'rnole'of N,N;' bistp-carbo'methoxybenz oybhexamethylene diamine; 0.3 mole of hexane'l,6-

' diol; a'nd0.5 ml. of catalyst solution, as described in the preceding example but containing'Z equivalentsof water .per equivalent of sodium; was heated at 245275; C. for 20 minutes under nitrogen and for 15 minutes at 275 "C. and Oil-0.5mm. pressure. The polymer was of exceptionally'good color and-had an inherent viscosity of L09 ancla meltingpoint off263 I was? 11 I "A mixture of 0.1; mole of 'N,N'-bis(p-carboisobutoxy- "benzoyl)hexamethyl'ene diamine-, 0.3 m1. of hexane-L6- diol and. water-containingcatalyst as described in the preceding example was heated at 245-275 C. for 20 minutes under nitrogen followed by 15 minutes at'275 C. and 0.1-0.5 mm. pressure. The resulting nearly pure white polymer had an inherent viscosity of 1.06 and a meltingpoint of 264 C. I t v Example 22 I 'For'eontinuous processingit is usually desirable -efiect the two stages of the condensation process in s'e- 'quence on the melt. At times,- however, it is desirable to prepare a prepolymer which can thenbe polymerized to the desired 'degree as needed by a powder build=up method. In a typical example, 52 g. of N,N'-bis'(pcarboisobutoxybenzoyl)hexarnethylene 'diarnine, I g.--'ofhexane-1,6-diohand 0.5 ml. of sodium.ethoxide-titanium 'butoxide solution were heated'at 245-275 ;C. vfor-"2'0 minutes and at 275 C. and 0.1 mm. pressureffdi'S Lininu'tes. The resulting ;low'-lmoleeular weight polymer was cooled 'undernitrogen and pulverized; The:powdetri was v I n then reheated' a't 235 C; and 0.1 mm. pressure' f r-onef hour to giveva. polymer havinggan: inherent viscosity of v .0.72 'and a. melting point of 260 C.

Example, I

for. 25 minutes at 242-248 C. and 0.1 mm; pressure to giveia polymer having an inherent'viscosity of. 1.07, and

a melting w Example 24 a 0.5 mole of N,Nbis(p-carboetho;y-]

anaemia ih nzoyl-l h leae'd e in fiet mo e of N biS eth be e'y )he m tllyl i di r in d @9 buta e-.lA-diol was-, pn n ed i awrdwq w th th process described in Example 1 l, The resulting polymer had ;;an inherent viscosity of 0.8 5 and a III i ting point of 270C. t

, Example V p I A mixture of 0.6 mole of N,N'-bis(p-carboethoxybenzoyl)ethylene diamine, 0.4 mole of N,N'-bis(-p-carboethoxybenzoyl)hexamethylene diamine and 3 moles of hexane-lfi-diol was condensed as described in Example 0.87 and'a melting point of 270 '11. The resulting polymer had an inherentviscosity of Thus, by means o'fthis invention, a new class of-highly v l5 useful polymers are provided which are of --part1eular utility in the manufacture of fibers, films and sheeting. The examples illustrate the unique combination of properties-possessed by the po lymers of the invention; and similar results ,are obtained-with the other polymers with- 20 in the scope of the invention as described herein. "By

.tneans of this invention, it 'is possible to obtain "in asingle polymer the advant'ageous characteristicsof both tbepolye rs and t e p ly m d s- I Iehange stageof the process-is usually carried out at axi temperatureabove 200 C. or above the melting point of the reactants. The second orpolymerization stage is also usually carried out above 200 C. and can be effected above the melting point of the glycol ester (and the polymer being formed) in the melt processror at a temperature not more than20 C; below the melting point of theglycol ester in the powder polymerization process. In the case of the polymers prepared from such glycols as tetramethylene, pentame thylene or hexarnethylene glycol, the temperature in the polymerization stage is preferably at least 240 C. The temperature employed earl be varied, of course, depending upon the polymerization time desired, the degree ofvacuurn. employed, the

melting point of the reactants and products and similar 0 variable factors. The temperature employed should be at least as high as the boiling point of the glycol liberated at the pressure employed and can therefore be at or about the boiling temperature of the glycol if-at- 'mospheric pressure is employed or if a lower pressure p is employed during thepolymerization stage. The-polymerization stage visdesirably carriedbut at pressures be- ;low :about 1mm. Hg for optimum results with pressures of 0.1-0.5 mm. or lower beingparticularly suitable. The

polymerization stage ,is continued until the polymer obtained is capable of forming fibers and films (including sheets) whichcan be oriented to give the-highly flexible andstrong shaped articles for which these polymersare particularly adapted.-

v Although the invention has been described in detail .55

with particular reference to certain preferred embodiments thereof, it will bevunderstood that variations and modifications can lbe effected within the. spirit and. scope of the invention-as described hereinabove and as defined-'in-the appended claims. p0 I -We claim: a v v .1. A :highly polymeric material capable of forming fibers and films, said rpolymericrmaterial having lalmelting point of at least 200?. Grand-an inherent viscosity of atleast 0.7 .and being fcirmedbyl reaction of, one molar proportion of a single dicarboxylatelrnonomer .withsat least two molar proportions of a single glycol at a temperature of at least 200 C., said polymeric material consisting essentiallyof a succession of recurring structural units of the formula are least 2 and an n em 9i.

mighties -sn il where n R, i an a t lsa erase. o '12-'1 -t=erb a wherein R and R' are-alltlylepeugroups of 2-10 carbon atoms, said polymeric material" resulting solely from the condensation polymerization of monomeric :material consisting of at leastfiones alkylene: glycol of {2710 :carbon atoms with a single dicarboxylic acid monomer having the functional 5 formula 1 th ei R is e a kyl n g out 2: 0 r rbog atom;-

.2- A h y p m ricmat orientable fibers and films a 1 id o s t g ess ntia lybfia s ssio 9 tee" structural units of the formula I increase: termite a d fsiipa ox le e mon m lm unti to have?!" pro or io Qr-a l a titws m ar PIP? 9 2$ 9 a lyce an s i s ndeas n be n t fie a a temp atur ef, at-lwstZOO vC- A hi hlspolymer mat i -sapahle Q p t i s .o i nta le fi rs an films and h vi atm lti tnsimv a le st QQ-.. and a h rentyiscg ty iet. leas 10: and persistin assent t 11y s ra susqess an 9t s=,urfin structural ni s of hee l mnla- L am-sewer ge} wherein -R and R arealkylen'e groups of -2-l0 carbon atoms, the combined number of'c'arbon atoms' ink and R being at least IZin-atleaet one quarter of said recurring structural units, said polymeric material resulting 9 .6 fro t .0t de.n t 9 p l er a i .Q m n meric ma e ial o s ing o a les t e 3lKYlF g y of 2-10 bon atoms andlas nsle ,dis r xylic acid m n me ha n etfunt tional or ula wherein R is ,anrua-lkylenc group of 12:10 $31 299; l l l said dicarboxylate monomer amountingitofonem lerzproportion for at leasttwo molarproportions .;of; sa i d glycol, and. said condensation being effected sat ;a.- temp eramre of at Ieast ZOOt-CM .I I r T References Citedin the'file of this patent we T$ ms. 2,011,250:

Carothers Eeb ;'16, ,1957 2,692,253 Holmen ,Q ot. 19, 1954 2, 9,508. Williams et a1 aalufl tll 1 2,851,443 

1. A HIGHLY POLYMERIC MATERIAL CAPABLE OF FORMING FIBERS AND FILMS, SAID POLYMERIC MATERIAL HAVING A MELTING POINT OF AT LEAST 200*C. AND AN INHERENT VISCOSITY OF AT LEAST 0.7 AND BEING FORMED BY REACTION OF ONE MOLAR PORPORTION OF A SINGLE DICARBOXYLATE MONOMER WITH AT LEAST TWO MOLAR PROPORTIONS OF A SINGLE GLYCOL AT A TEMPERATURE OF AT LEAST 200*C., SAID POLYMERIC MATERIAL CONSISTING ESSENTIALLY OF A SUCCESSION OF RECURRING STRUCTURAL UNITS OF THE FORMULA 